Composition including an item and an encoded optical identification element that is physically associated with the item

ABSTRACT

A composition including an item and an optical identification element that is physically associated with the item. The optical identification element includes a binder material and one or more materials embedded in the binder material. The one or more materials provides a composite X-ray diffraction pattern when illuminated by an X-ray beam. The composite X-ray diffraction pattern being indicative of a code. The code relating to information about the item.

TECHNICAL FIELD

This invention relates to optical identification, and more particularlyto a method and apparatus for labeling using optical identificationelements characterized by X-ray diffraction.

BACKGROUND ART

It is often desirable to uniquely label or identify items, such as largeor small objects, plants, and/or animals for sorting, tracking,identification, verification, authentication, or for other purposes. Forexample, in a form of chemical synthesis in combinatorial chemistryknown as “solid phase” chemical synthesis, encoded beads or particlesare used as a solid support for the synthesis of chemicals and orchemical libraries. The encoded beads or particles are used identify theattached chemicals.

In another example, in a DNA/genomic sequencing assay commonly referredto as a “random bead assay”, known DNA sequences (probes) are attachedto encoded beads or particles. The beads are then mixed with a labeledtarget analyte, and segments of the DNA sequence of the labeled targetanalyte will selectively bind to complementary DNA segments of theprobe. The known probes are then spatially separated and examined forfluorescence. The beads that fluoresce indicate that the DNA sequencestrands of the target analyte have attached or hybridized to thecomplementary DNA on that bead. The DNA sequences in the target analytecan then be determined by identifying the code on the bead, whichuniquely identifies the complementary DNA (or cDNA) sequence of eachprobe. In addition the level of fluorescence is indicative of how manyof the target molecules hybridized to the probe molecules for a givenbead.

Existing technologies for uniquely labeling or identifying items, suchas bar codes, electronic microchips/transponders, radio-frequencyidentification (RFID), and fluorescence (or other optical techniques),are often inadequate. For example, existing technologies may be toolarge for certain applications, may not provide enough different codes,may require specific alignment of particles to the detector, or cannotwithstand harsh environments, e.g., harsh temperature, pressure,chemical, nuclear and/or electromagnetic environments.

Therefore, it would be desirable to obtain a labeling technique thatprovides the capability of providing many codes (e.g., greater than 1million codes), that can be made very small, that can withstand harshenvironments, and/or be independent of orientation with respect to thedetector.

SUMMARY OF THE INVENTION

Objects of the present invention include provision of a labelingtechnique that allows for a large number of distinct codes, can be madevery small, code is readable independent of orientation, and/or canwithstand harsh environments.

According to a first aspect of the present invention, an opticalidentification element for identifying an item comprises a bindermaterial and one or more materials embedded in the binder material. Theone or more materials provide an encoded composite X-ray diffractionpattern when illuminated by an X-ray beam. The encoded composite X-raydiffraction pattern is indicative of the item.

According to a second aspect of the present invention, a method oflabeling an item comprises: selecting at least one material from aplurality of materials having differing X-ray diffraction patterns;embedding the at least one material in a binder material to form atleast one optical identification element; and physically associating theat least one optical identification element with the item. The at leastone material provides an encoded composite X-ray diffraction patternwhen illuminated by an X-ray beam, with the encoded composite X-raydiffraction pattern being indicative of the item.

According to a third aspect of the present invention, a method ofidentifying an item comprises: illuminating an optical identificationelement physically associated with the item using an X-ray beam;detecting a composite X-ray diffraction pattern from the illuminatedoptical identification element; and decoding the composite X-raydiffraction pattern to identify the item. In various embodiments, thedecoding includes identifying at least a portion of Debye-Scherrerdiffraction patterns in the composite X-ray diffraction pattern.

In various embodiments of the above aspects of the present invention,the encoded composite X-ray diffraction pattern is indicative of abinary or higher order. The number of bits in the binary code maycorrespond to the number of unique Debye-Scherrer diffraction patternsin the encoded composite X-ray diffraction pattern. The binary code maybe arranged in a protocol including one or more error-check bits and aplurality of data bits.

In various embodiments of the above aspects of the present invention,the one or more materials is selected from powdered crystal materials.The binder material may be selected from glass, plastic, one or morepolymers, and combinations including one or more of the foregoing.

In various embodiments of the above aspects of the present invention,the optical identification element is shaped as a microbead or amacrobead. Alternatively, the binder material may be in the form of athread or fiber.

In various embodiments of the above aspects of the present invention,the item is selected from the group, comprising: large or small objects,products, solids, powders, liquids, gases, plants, currency, ID cards,minerals, cells and/or animals. The item may be a chemical or a DNAsequence.

The foregoing and other objects, features and advantages of the presentinvention will become more apparent in light of the following detaileddescription of exemplary embodiments thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram illustrating a method for encoding anoptical identification element in accordance with various embodiments ofthe present invention.

FIG. 2 depicts front and back Debye-Scherrer diffraction patterns for anoptical element including powdered crystals in accordance with variousembodiments of the present invention.

FIG. 3 depicts a Debye-Scherrer camera.

FIG. 4 depicts encoded X-ray diffraction patterns in accordance withvarious embodiments of the present invention.

FIG. 5 shows a bit format for a code in an optical identificationelement of the present invention.

FIG. 6 illustration (a) shows an X-ray diffraction pattern for powderedaluminum, and illustration (b) is a plot of intensity and d spacing forvarious materials.

FIG. 7 is a schematic diagram of a system for identifying an item havingone or more optical identification elements physically associatedtherewith in accordance with various embodiments of the presentinvention.

FIG. 8 illustrations (a)-(d) show various transparent items that can belabeled with an optical identification element of the present invention.

FIG. 9, illustrations (a)-(c) show various integrated circuits orsilicon wafers, that can be labeled with an optical identificationelement of the present invention.

FIG. 10 shows a cell or the like disposed on an optical identificationelement.

FIG. 11, illustrations (a)-(d) show fluids or powders that can belabeled with an optical identification element of the present invention.

FIG. 12, illustrations (a)-(v) show various other items that can belabeled with an optical identification element of the present invention.

FIG. 13 illustrations (a) and (b) depict the optical identificationelement being applied as a paint or powder coating.

FIG. 14 is a flow chart for a chemical split and pool synthesisapparatus in accordance with various embodiments of the presentinvention.

FIG. 15 is a diagram of a chemical split and pool synthesis apparatus inaccordance with various embodiments of the present invention.

FIG. 16 is a flow chart of a method of attaching a substance to anoptical identification element, performing an assay and analyzing theoptical identification element in accordance with various embodiments ofthe present invention.

FIG. 17 is a side view of an optical identification element having asubstance attached to the outer surface thereof in accordance withvarious embodiments of the present invention.

FIG. 18 is a side view of an optical identification element having asubstance attached to the outer surface thereof, in accordance withvarious embodiments of the present invention.

FIG. 19 is a schematic view of a plurality of optical identificationelements having different identification or codes and coated withdifferent probe substances disposed in a cell with a plurality of testsubstances, in accordance with various embodiments of the presentinvention.

FIG. 20 is a schematic view of plurality of optical identificationelements after the performance of an assay, aligned in a plurality ofgrooves, disposed on a substrate, and a bead detector that scans eachoptical identification element for determining the code and fluorescenceof each optical identification element, in accordance with variousembodiments of the present invention.

FIG. 21 is a schematic view of a flow cytometer including a system foridentifying an item having one or more optical identification elementsphysically associated therewith in accordance with various embodimentsof the present invention.

FIG. 22 is a side view of an optical identification element after theperformance of an assay, and a schematic view of a bead detector thatdetermines the code and fluorescence of the optical identificationelement, in accordance with various embodiments of the presentinvention.

FIG. 23 is a cross-sectional view of an X-ray diffraction encoded and adiffraction grating encoded identification element in accordance with anembodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Referring to FIG. 1, an encoded optical identification element (element)8 for identifying an item is shown. The optical identification element 8is a composite structure formed from one or more materials 1-4 embeddedin a binder material 5. In the example shown in FIG. 1, the opticalidentification element 8 is in the shape of a bead, and four differentmaterials 1-4 are embedded in the binder material 5 to form the bead. Aswill be described in further detail hereinafter, any number of materialsmay be used, and the optical identification element 8 may take anyconvenient shape.

Each of the materials 1-4 provides a unique X-ray diffraction pattern,as indicated at 9-12 respectively, when illuminated by an X-ray beam. Inthe embodiment shown, the X-ray diffraction patterns 9-12 are rings 14,each of which are portions of a Debye-Scherrer diffraction pattern.

When the materials 1-4 are embedded in the binder material 5 to form theoptical identification element 8, the X-ray diffraction patterns 9-12 ofthe materials 1-4 produce a composite X-ray diffraction pattern 13 forthe optical identification element 8. In the present invention, thecomposite X-ray diffraction pattern 13 is encoded by the selection andomission of one or more of the different materials 1-4. A code 58provided by the composite X-ray diffraction pattern 13 is used toidentify an item physically associated with the optical identificationelement 8. By physically associated, it is meant that the opticalidentification element 8 is attached to, embedded in, disposed proximateto, mixed with, or otherwise located in some relationship to the item.

Preferably, each of the materials 1-4 is a powdered crystal materialhaving a well-defined Debye-Scherrer X-ray diffraction pattern. By a“powdered” crystal material it is meant that the material is formed fromsome ten or more randomly oriented single crystals. For such materials,a collimated, monochromatic, incident X-ray beam 18 is diffracted inaccordance with Braggs law to produce diffracted beams lying on thesurface of several cones 22 as shown in FIG. 2( a). The cones 22 mayemerge in all directions, forward (in the direction of the X-ray beam18) and backward (in a direction opposite that of the X-ray beam 18).When the cones 22 are projected onto planes 26 and 28, the diffractionpattern includes one or more concentric rings 14 as shown in FIGS. 2( b)and 2(c). FIG. 2( b) depicts the backward plane 26, and FIG. 2( c)depicts the forward plane 28. The diffraction pattern (e.g., rings 14)formed on the forward plane 28 or the diffraction pattern (e.g., rings14) formed on the backward plane 26, or both, may be used in theencoding method of the present invention.

The diffraction patterns may be detected using any known opticaldetectors 30 (e.g., a charge coupled device (CCD) detector, film, imageplate detectors, among others) positioned at the planes 26 and 28. Suchoptical detectors 30 may have apertures 32 disposed therethrough forallowing passage of the incident X-ray beam 18 and the transmittedportion of X-ray beam 18 (indicated at 18′).

Referring to FIG. 3, it is contemplated that any portion of the cones 22may be used to form an X-ray diffraction pattern. For example, FIG. 3(a) depicts a Debye-Scherrer camera, in which an optical detector 30(e.g., a charge coupled device (CCD) detector, film, image platedetectors, among others) is disposed concentrically around theidentification element 8. FIG. 3( b) depicts the detector 30 in astraightened state. As can be seen in FIG. 3( b), the X-ray diffractionpattern captured by the detector 30 is a portion of the rings 14, whichappear on the detector as arcs or “lines”. All or part of the portion ofthe rings 14 may be used in the encoding method of the presentinvention.

Referring again to FIG. 1, combining one or more powdered crystalmaterial in the binder material 5 will produce an element 8 with acomposite X-ray diffraction pattern 13 made up of one or morewell-defined rings 14 (or portions of rings 14), as shown in FIG. 1.Selection and omission of certain materials allow the combined X-raydiffraction pattern 13 of the optical identification element 8 to beencoded, with the presence or absence of each of the rings 14 (orportions of rings 14) indicating a binary “1” or “0” in the code 58, asindicated in FIGS. 4 a-c. While FIGS. 1 and 4 a-c show only fivedifferent codes, it will be appreciated that the four materials 1-4 inthe example of FIG. 1 can be used to generate 16 different codes 58 byvirtue of either their presence or absence. It is contemplated that thenumber of materials used is a function of the number of different codesneeded to identify the item. For example, the use of 10 materialsprovides 1024 different codes, and N materials provides 2^(N) differentcodes. Advantageously, the present invention provides a labelingtechnique that allows for a large number of distinct codes.

While the code 58 is shown as a binary code, it is contemplated thathigher order codes may be used. For example, by providing N codingidentifiers, each having M distinguishable states, M^(N) unique codescan be created. Where M=2 (e.g., the two states could be the presence orabsence of the materials 1-4), the code 58 is the base 2 or binary codedescribed above. In the case of M=3 (e.g., where the three states couldbe three distinguishable intensity levels for a range of inter atomic(D) spacings, the code 58 would be defined by a base 3 code. It is alsocontemplated that code 58 may be defined by analog coding methods; forexample, the signature of each component of the entire compositespectrum 13 may be analyzed.

Referring to FIG. 5, the code 58 may be a simple code or may be a morecomplex code having many pieces of information located in the code 58.In addition, the code 58 may have checks within the code to ensure thecode 58 is read correctly. It can be viewed as a serial digital message,word, or frame consisting of N bits.

In particular, there may be start and stop bits 869, 871, respectively.The start and stop bits may each take up more than one bit location ifdesired. In addition there may be an error check portion of the message,such as a check sum or CRC (cyclic redundancy check) having apredetermined number of bits, and a code section 873 having apredetermined number of bits. The error check portion ensures that thecode 8 which is obtained from the bead is accurate. Accordingly, havinga large number of bits in the element 8 allows for greater statisticalaccuracy in the code 8 readout and decreases the likelihood of providingerroneous data. Accordingly, if a code 8 cannot be read without anerror, no data from that code 8 will be provided, avoiding an erroneousresult. Any known techniques for digital error checking for single ormulti-bit errors may be used.

The code section 873 may be broken up into one or more groups of bits,for example, three bit groups 863,865,867, each bit group containinginformation about the bead itself or the item attached to the bead orhow the bead is to be used, or other information. For example, the firstbit group 863 may contain information regarding “identifying numbers”,such as: lot number, quality control number, model number, serialnumber, inventory control number; the second bit group 865 may contain“type” information, such as: chemical or cell type, experiment type,item type, animal type; and the third bit group 867 may contain “date”information, such as: manufactured date, experiment date, creation date,initial tracking date. Any other bit groups, number of bit groups, orsize of bit groups may be used if desired. Also, additional error orfault checking can be used if desired.

In particular, for a product manufacturing application, the code section873 may have the serial number, the lot number, date of manufacture,etc. or have other information that identifies the item and/orinformation about the item. For a chemical or assay application, thecode section 873 may have information about the chemical attached to thebead, the date and/or time of creation of the chemical or experiment, orother information of interest.

FIG. 6 illustration (a) shows an X-ray diffraction pattern for powderedaluminum, which comprises four rings 14. Other suitable materialsinclude, for example, aluminum oxide, calcium carbonate, and nickelsulfide, as shown in FIG. 6 illustration (b).

Referring again to FIG. 1, the binder material 5 is preferably amaterial that does not diffract the X-ray beam 18 (FIGS. 2 and 3), orwhich diffracts the X-ray beam 18 in a known (i.e., filterable) manner.For example, the binder material 5 may be selected from glass, plastic,one or more polymers, and combinations including one or more of theforegoing. In other examples, the binder material 5 may be made of anyone or more of various glasses, e.g., silica, phosphate glass,borosilicate glass, or other glasses, or made of glass and plastic, orsolely plastic.

Referring to FIG. 7, a system for identifying an item having one or moreoptical identification elements 8 physically associated therewith isshown generally at 15. The system 15 has the necessary optics,electronics, software and/or firmware to perform the functions describedherein. The system 15 may include any commercially available X-raydiffractometer.

Referring to FIGS. 1 and 7, the system 15 includes a light source 16, anoptical detector 30, a computer 22, and an output device 23. The lightsource 16 provides a collimated, monochromatic X-ray beam 18, which maybe triggered or otherwise controlled by the computer 22. The opticaldetector 30 (e.g., a multichannel charge-coupled device array) issituated to receive the composite X-ray diffraction pattern 13 producedby the illuminated optical identification element 8 and provide anoutput signal indicative of this composite X-ray diffraction pattern 13.In the embodiment shown, the optical detector 30 is arranged to receiveonly the back reflected portion of the composite X-ray diffractionpattern 13. As previously discussed, the optical detector 30 may bearranged to receive all or a portion of any part of the composite X-raydiffraction pattern 13. For example, the optical detector 30 may bearranged as described herein with reference to FIGS. 2 or 3.

The computer 22 receives the output signal from the optical detector 30,decodes the composite X-ray diffraction pattern 13, and provides abinary or higher order code 58 indicative of the composite X-raydiffraction pattern 13. The decoding may be performed by identifying atleast portions of unique Debye-Scherrer diffraction patterns in thecomposite X-ray diffraction pattern 13. A lookup table, database, or thelike may then be used to determine the item associated with the code 58,and the name of the item may then be displayed on the output device 23.

Referring again to FIG. 1, the optical identification element 8 may beof any convenient shape. For example, the optical identification element8 may be shaped as a bead, such as a microbead (or microelement,micro-particle, or encoded particle) having at least one dimension ofless than about 1000 microns or a macrobead having at least onedimension of greater than about 1000 millimeters. Alternatively, thebinder material may be in the form of a thread or fiber or may be in theform of a paint or coating.

As shown in FIGS. 8-12, the encoded element 8 may be used to label anydesired item, such as large or small objects, products, solids, powders,liquids, gases, plants, pharmaceuticals (drugs), minerals, and/oranimals, or any combination of one or more thereof. The label may beused for many different purposes, such as for sorting, tracking,identification, verification, authentication,anti-theft/anti-counterfeit, security/anti-terrorism, or for otherpurposes. In a manufacturing environment, the elements 8 may be used totrack inventory for production information or sales of goods/products.As shown in FIG. 13, the encoded element 8 may be in the form of a paintor powder coating. The paint or powder coating can be applied tovirtually any surface. For example, the paint or powder coating may beapplied to a vehicle such as a boat or car, or a container transportedby ship.

Also, the X-ray diffraction material or substances of the presentinvention may be incorporated into an ink, paint, powder or any otherprinting substance that allows printed documents to be uniquelyidentified by the X-ray diffraction pattern emitted in response to theincident X-ray. In that case, the text itself would emit a predetermineddiffraction pattern that uniquely identifies the document. Such materialcould also be incorporated into the paper, document, or package makingprocess, e.g., the pulp or the coatings, that uniquely identifies theproduct made.

For any of the labeled items described herein, the encoded elements 8may be tiny discrete microbeads (0.01 micrometers to 1000 micrometerslong) embedded into the surface of the item or the encoded element 8 maybe a long strand of glass or plastic fiber that is woven, inserted,impressed, or injected into the item being labeled. Alternatively, inthe appropriate cases, the materials 1-4 may be impressed directly intothe material. In any case, the properties of the encoded element 8 donot change. For labeled items that are pliable, bendable, or flexible,the element 8 may be made of a bendable material, such as a polymer orplastic. Also, if the item material is soft or compliant the beads maybe pressed, pushed, hammered or shot into the material.

In general, the encoded elements 8 may be used to label any products orcomponents within a product and may be used for productmanufacturing/production identification.

Referring to FIG. 8, illustrations (a)-(d), encoded elements 8 may beused to label glass or plastic items, such as microscope slides 811,test tubes 813, beakers 815, cookware 817, storage containers and/orcovers, multi-well plates, micro-well plates, plastic bags, windshields,windows, glasses, contact lenses, other lenses, optical components,tape, bottles, displays, display cases, watch faces, mirrors, sample orpietri dishes, or any other item made of a material that is transparentor substantially transparent to the incident X-ray 24 and reflectedX-ray 27 used for read the code in the encoded elements 8. The inventionmay be used to identify such glass or plastic items by embedding thematerials 1-4 directly into the item or by embedding into or otherwiseattaching the encoded elements 8 to the item. In the case where thematerials 1-4 are embedded directly into the item, the material formingthe item is the binder material 5 and is preferably a material that doesnot affect the X-ray diffraction pattern provided by the materials 1-4,or which affects the X-ray diffraction pattern in a known (i.e.,filterable) manner.

Referring to FIG. 9, illustrations (a) and (b), the encoded elements 8may be used to label micron size products, such as, microcircuitscomputer chips, integrated circuits (IC's), or other small products orportions thereof. Referring to FIG. 9, illustration (c), the elements 8may also be used to label silicon wafers 59 or small portions or regions57 thereof before being cut into small devices or microcircuits.

Referring to FIG. 10, the elements 8 may be used to label any single ormultiple cells 101 that are attached to or otherwise disposed on theelement 8. The cells 101 may include: molecules, particles, elements,compounds, organisms, atoms, chemicals, acids, bases, nucleic acids,chemical libraries, DNA, polynucleotides, oligomers, RNA, proteins,peptides, polymers, hydrocarbons, or other cells. The cells 101 may bealive or dead, organic or inorganic, and may be individual or groups orchains of cells and may change or mutate over time.

Referring to FIG. 11, illustrations, (a)-(d), the encoded elements 8 maybe used to label a liquid or liquid products located in a container 801or in an open or closed flowing pipe or conduit 803, 805 respectively.In that case, the elements 8 are mixed with the liquid. In addition, theelements 8 may also be used to label powders, such as powdereddetergent, dirt, pulverized coal, gunpowder, anthrax, or any otherpowders located in a container 807, or in an open or closed flowing pipeor conduit 803,805, respectively. Also, the elements 8 may be used tolabel or identify any combination of fluids (liquids and/or gases)and/or powders. Also, the elements 8 may be used to label gases, such asgases in containers or gases flowing in a pipe or conduit, or gaseousby-products of reactions, such as combustion exhaust or other exhaust.Also, the elements 8 may be used to label liquid particles or dropletsin gas, such as steam. The elements 8 may be used to track the flow of aliquid, powder, gas, etc. in an industrial plant to determine where theliquid is flowing or has flown.

The elements 8 may be removed from a fluid, powder and/or gas solutionor mixture other material by electro-magnetic attraction (if theelements 8 are electro-magnetic), skimmed off the surface (if theelements 8 are less dense than the solution, i.e., buoyant orsemi-buoyant), or from settling to the bottom of a container (if theelements 8 are more dense than the solution), or by filtering thesolution with a strainer or filter.

The elements 8 can placed in a fluid or powder and the fluid or powderis used for labeling an item. For example, the elements 8 may be mixedwith paint (or other adhesive fluid) and sprayed on an item, such as acar or boat (see FIG. 12, illustrations (b) and (c)) or any other itemthat can be sprayed or painted. The same may be done with a dry powderthat is sprayed on a newly painted or otherwise adhesive surface, orwith an adhesive powder that is sprayed on a dry, or painted or adhesivesurface.

Referring to FIG. 12, illustrations (a), (b), (c), (f), (g), and (h), inparticular, the encoded elements 8 may be used to label large and/orvaluable items such as cases 841 (e.g., suitcases, briefcases, garmentbags, and the like), cars 831, boats 833, paintings 835, china 837,jewelry 839, and the like. Also, the elements 8 may be used as a way ofputting the vehicle identification number (VIN) or other similaridentification information in a hidden location and/or in many locationson an item that can only be read by the proper equipment.

Referring to FIG. 12, illustrations (d), (e), and (r), the encodedelements 8 may also be used to label currency 829, coins, bills, orcredit cards. Also, the elements 8 may be used an alternative oraddition to magnetic strips currently used on many types of cards 825,e.g., access cards, key cards, ID cards, debit cards, credit cards, andthe like. In addition, the elements 8 may be used as part of a key 827.

Referring to FIG. 12, illustration (i), the elements 8 may be used tolabel food containers 847 and the like.

Referring to FIG. 12, illustrations (j) and (l), the elements 8 may beused to label building materials 843, e.g., wood, pressboard, compositeboards (e.g., made of wood, plastic, and/or metal particles), sheetrock,wallboard, wallpaper, molding, tiles and the like or other buildingmaterials. Similarly, the elements 8 may be used to label furniture orother home or office furnishings 845.

Referring to FIG. 12, illustrations (m), (o), and (p), the encodedelements 8 may be used to label any animals 649, creatures,people/humans 855, and/or plants, or parts thereof 853. Such a labelcould be used in addition to or instead of fingerprints, retina scans,DNA or other identification techniques or labels.

Referring to FIG. 12, illustrations (n) and (q), the encoded elements 8may be used to label documents 857, books 851, and/or packages.

Referring to FIG. 12, illustrations (s) and (t), the encoded elements 8may be used to label weapons, ammunition, explosive devices, guns 819,artillery, bullets 821, mortar, grenades, missiles, torpedoes,projectiles, fireworks, bombs, spacecraft, aircraft, satellites, jetengines, submarines and tanks.

Referring to FIG. 12, illustration (u), the encoded elements 8 may beused to label clothing 823, garments, uniforms, linens, leather,footwear, headgear, or textiles.

Referring to FIG. 12, illustration (v), the encoded elements 8 may beused to label storage media, such as compact discs and digital videodiscs (DVD's), or any other devices that uses light to read information,video or audio tapes, disc drives, and the like.

Referring to FIG. 13, the optical elements described herein may be usedto synthesize chemicals in a known split and pool synthesis technique,such as that described in U.S. patent application Ser. No. 10/661,254(CyVera Docket No. CC-0043), filed Sep. 12, 2003, which is incorporatedby reference herein in its entirety. In particular, a known split andpool bead based synthesis process 801, may be performed starting with astep 800 where a predetermined number M of compounds or chemicals areprovided each in a separate bin or container and at step 802 where apredetermined number X of microbeads 8 are provided each having its ownunique code. Steps 800, 802 are material preparation steps and can bedone in either order. After the materials are prepared, a step 803combines or pools all the beads together. Then, a step 804 determinesthe code for each microbead 8. This step can be skipped on the firsttime through the process if it is desired to randomly split up the beadsinto groups, i.e., to not split the groups up by code on bead during thefirst run. Next a step 806 sorts the beads based on its code anddeposits the bead into the appropriate bin for the chemical to be addedto the bead.

Next, a step 808 tests to see if the chemical synthesis is complete foreach bead. If not the process goes back to step 803 where the remainingbeads are recombined or re-pooled and the process starts again. The loop814 repeats a predetermined number of times N, where each time throughthe loop 814 another chemical is added to each of the beads. If certainbeads are to have fewer chemicals than others, then certain beads willdrop out of the process before others. When the step 808 concludes thatone or more beads have completed their synthesis process, a step 812logs the completion of that bead and the remainder of the beads continueuntil all desired chemicals have synthesized on the beads.

For example, for M=4 compounds and N=10 chemicals to add to each bead,the total number of different codes needed would be 1,048,576 or M^(N)and if there will be only one bead with each desired chemical (i.e., noredundancy), then the number of beads X would also be M^(N)=1,048,576.

Referring to FIG. 15, an automated synthesis machine is shown forsynthesizing a chemical having four different possible compounds orcells or molecules (e.g., GCAT for a DNA synthesis), where a main bin830 receives or pools all the beads 8 and provides the beads 8 to asorting machine 832, which performs the sorting step 806 in the loop814. The sorting may be accomplished using the system 15 describedherein to identify the beads. In addition the machine 832 deposits thebeads in the proper bins 834,836, 838,840, having the bases G, C, A, T,respectively. Any other four chemicals can be used if desired. Once thespecific base has been attached to a bead it is dropped or placed in adevice which transports the beads back into the main bin 830 forresorting by the machine 832. When synthesis has been completed on agiven bead the machine deposits the completed bead in a done bin 844.

If it is desired to produce multiple of the same chemical on separatebeads this can be done by having multiple beads with the same code, orpresetting certain groups of codes to have the same chemicalcomposition. In that case, each of these beads may go to the same binsin the same order as a group.

The present invention may be used with any known combinatorialchemistry, chemical synthesis process, or synthesizing labeledcombinatorial chemistry libraries, and are especially adaptable to solidphase synthesis, for example: U.S. Pat. No. 6,417,010, “Methods andApparatus for Synthesizing Labeled Combinatorial Chemistry Libraries”,U.S. Pat. No. 6,558,904 entitled “Method for producing structured,self-organized molecular monolayers of individual molecular species, inparticular substance libraries”; U.S. Pat. No. 6,541,276 entitled“Methods for solid-phase synthesis of hydroxylamine compounds andderivatives and combinatorial libraries thereof”; U.S. Pat. No.6,541,211 “Apparatus and method for synthesizing combinationallibraries”; U.S. Pat. No. 6,528,324 entitled “Apparatus forpre-determined mass sorting of positional-encoded solid phase synthesissupports”; U.S. Pat. No. 6,506,558 entitled “Very large scaleimmobilized polymer synthesis”; U.S. Pat. No. 6,495,539 entitled“B-lactam-like chaperone inhibitors”; U.S. Pat. No. 6,468,740 entitled“Cyclic and substituted immobilized molecular synthesis”; U.S. Pat. No.6,417,010 entitled “Methods and apparatus for synthesizing labeledcombinatorial chemistry libraries; U.S. Pat. No. 6,410,643 entitled“Solid phase synthesis method and reagent”; U.S. Pat. No. 6,410,342entitled “Method and apparatus for controlled photoelution”; U.S. Pat.No. 6,387,636 entitled “Method of shielding biosynthesis reactions fromthe ambient environment on an array”; U.S. Pat. No. 6,372,885 entitled“Solid-phase technology for the preparation of amides”; U.S. Pat. No.6,368,874 entitled “Methods for hard-tagging an encoded syntheticlibrary”; U.S. Pat. No. 6,362,009 entitled “Solid phase synthesis ofheterocycles”; U.S. Pat. No. 6,346,423 entitled “Methods andcompositions for producing biopolymeric arrays”; U.S. Pat. No. 6,329,210entitled “Method and apparatus for high volume polymer synthesis”; U.S.Pat. No. 6,294,694 entitled “Matrix metalloproteinase inhibitors andmethod of using same”; U.S. Pat. No. 6,274,385 entitled “Attached tagsfor use in combinatorial chemistry synthesis”; U.S. Pat. No. 6,265,228entitled “Process for preparing combinatorial amide alcohol libraries”;U.S. Pat. No. 6,251,595 entitled “Methods and devices for carrying outchemical reactions”; U.S. Pat. No. 6,127,190 entitled “Method forproducing combinatorial libraries having a predetermined frequency ofeach species of test compound”; U.S, Pat. No. 5,929,208 entitled“Methods for electronic synthesis of polymers”; U.S. Pat. No. 5,886,186entitled “Synthesis of substituted N-heteroaromatic compounds andmethods of use thereof”; U.S Pat. No. 5,885,837 entitled “Very largescale immobilized polymer synthesis using mechanically directed flowpaths”; U.S. Pat. No. 5,859,191 entitled “Method for the site-specificmodification of peptide alpha amines”; U.S. Pat. No. 5,763,263 entitled“Method and apparatus for producing position addressable combinatoriallibraries”; U.S. Pat. NO. 5,712,171 entitled “Method of generating aplurality of chemical compounds in a spatially arranged array”; U.S.Pat. No. 5,690,894 entitled “High density array fabrication and readoutmethod for a fiber optic biosensor”; U.S. Pat. No. 5,545,568 entitled“Solid phase and combinatorial synthesis of compounds on a solidsupport”; U.S. Pat. No. 5,545,531 entitled “Methods for making a devicefor concurrently processing multiple biological chip assays”; U.S. Pat.No. 5,539,083 entitled “Peptide nucleic acid combinatorial libraries andimproved methods of synthesis”; U.S. Pat. No. 5,384,261 entitled “Verylarge scale immobilized polymer synthesis using mechanically directedflow paths”; U.S. Pat. No. 5,288,514 entitled “Solid phase andcombinatorial synthesis of benzodiazepine compounds on a solid support”;U.S. Pat. No. 5,264,563 entitled “Process for synthesizingoligonucleotides with random codons”; U.S. Pat. No. 5,010,175 entitled“General method for producing and selecting peptides with specificproperties”; U.S. Pat. No. 6,465,192 entitled “Compounds and methods forthe inhibition of protein-protein interactions”; U.S. Pat. No. 6,440,669entitled “Methods for applying small volumes of reagents”; U.S. Pat. No.6,406,844 entitled “Very large scale immobilized polymer synthesis”;U.S. Pat. No. 6,329,010 entitled “Method and apparatus for high volumepolymer synthesis”; U.S. Pat. No. 6,316,623 entitled “Ethylenediaminecompound libraries”; U.S. Pat. No. 5,780,241 entitled “Complex chemicallibraries”; U.S. Pat. No. 5,712,171 entitled “Method of generating aplurality of chemical compounds in a spatially arranged array”; U.S.Pat. No. 5,593,853 entitled “Generation and screening of synthetic druglibraries”; U.S. Pat. No. 6,569,631 entitled “Microplate thermal shiftassay for ligand development using5-(4″dimethylaminophenyl)-2-(4′-phenyl)oxazole derivative fluorescentdyes”; U.S. Pat. No. 6,503,759 entitled “Complex combinatorial chemicallibraries encoded with tags”; U.S. Pat. No. 6,492,125 entitled “Methodto assess library X library interactions”; U.S. Pat. No. 6,457,807entitled “Mass-based encoding and qualitative analysis of combinatoriallibraries”; U.S. Pat. No. 6,455,263 entitled “Small molecule libraryscreening using FACS”; U.S. Pat. No. 6,096,496 entitled “Supportsincorporating vertical cavity emitting lasers and tracking apparatus foruse in combinatorial synthesis”; U.S. Pat. No. 5,770,455 entitled“Methods and apparatus for synthesizing labeled combiatorial chemistrylibraries”; U.S. Pat. No. 5,751,629 entitled “Remotely programmablematrices with memories”; U.S. Pat. No. 6,537,504 “Method and apparatusfor concurrent and sequential multi-step reactions for producing aplurality of different chemical compounds”; U.S. Pat. No. 6,468,806“Potential masking systems and methods for combinatorial librarysynthesis”; U.S. Pat. No. 6,429,027 “Composite arrays utilizingmicrospheres”; U.S. Pat. No. 6,420,169 “Apparatus for formingpolynucleotides or polypeptides”; U.S. Pat. No. 6,448,443 “Synthesis ofcombinatorial libraries of compounds reminiscent of natural products”;U.S. Pat. No. 5,840,485 “Topologically segregated, encoded solid phaselibraries”.

Referring to FIGS. 16-21, the optical identification element (ormicrobead) 8 may be functionalized by coating or attaching a desiredprobe 76, such as a compound, chemical or molecule, as described in U.S.patent application Ser. No. 10/661,031 (CyVera Docket No. CC-0039A)filed Sep. 12, 2003, which is incorporated by reference herein in itsentirety. The probe 76 is then used in an assay as an attractant forcertain complimentary compounds, chemicals or molecules, otherwise knownas a “target” analyte 52-54 (see FIG. 19). This capability to uniquelyencode a large number of microbeads 8 with a corresponding unique probe76 attached thereto enables these functionalized microbeads 72 to bemixed with unknown “target” analytes 52-54 to perform a multiplexedexperiment. The procedure 40 for performing such a multiplexed assay orexperiment includes the steps of producing (step 42) the encoded opticalidentification element (microbead) 8, as described hereinbefore, andfunctionalizing (step 44) the substrate 10 of the microbead 8 bycoating/depositing/growing it with a probe 76 that will react in apredetermined way with “target” analytes 52-54. An assay is thenperformed (step 46) with a plurality of functionalized microbeads 72with different identification codes 58 at the same time. In step 48, thefluorescence of the functionalized microbeads 72 is analyzed, and thefunctionalized microbead 72 is read to determine the code 58 thereof tothereby determine which “target” analytes 52-54 are present in thesolution 60.

In FIGS. 17 and 18, a functionalized microbead 72 is shown, wherein thesubstrate 10 of the microbead 8 is coated with a probe 76 and used in anassay or as an attractant for certain “target” analytes 52-54 (see FIG.19). In one embodiment shown in FIG. 17, the microbead 8 is coated witha linker molecule or complex 62 as is known in the art. A moleculargroup 64 is attached to the probe 76 to enable the probe to be bonded tothe linker molecule or complex 62, and thus to the microbead 8 to formthe functionalized microbead 72. The probe 76 may include one of anOligonucleitides (oligos), antibodies, peptides, amino acid strings,cDNA, RNA, chemicals, nucleic acid oliomers, polymers, biological cells,or proteins. For example, the probe 76 may comprise a single strand ofDNA (or portion thereof) and the “target” analyte 52-54 comprises atleast one unknown single strand of DNA, wherein each different “target”analyte has a different DNA sequence.

In some instances as shown in FIG. 18, the probe 76 may be attacheddirectly to the substrate 10 of the microbead 8, or directly synthesized(or grown) thereon, such as via phosphoramidite chemistry. Examples ofsurface chemistry for the functionalized microbeads 72 includeStreptavidin/biotinylated oligos and Aldehyde/amine modified oligos.Further, the microbead may be coated with a blocker of non-specificbinding (e.g., salmon sperm DNA) to prevent bonding of analytes 52-54(e.g. DNA) to the non-functionalized surface 66 of the functionalizedmicrobeads 72.

Referring to FIG. 19, an assay is performed by adding a solution 60 ofdifferent types of “target” analytes 52-54 into a cell or container 70having a plurality of functionalized microbeads 72-74 disposed therein.As discussed in step 46 of FIG. 16, the functionalized microbeads 72-74placed in the cell 70 have different identification codes 58 thatcorrespond to unique probes 76-78 bonded thereto. For example, allfunctionalized microbeads 72 disposed within the cell 70 having anidentification code of 12345678 is coated with a unique probe 76. Allfunctionalized microbeads 73 disposed within the cell 72 having anidentification code of 34128913 is coated with a unique probe 77. Allfunctionalized microbeads 77 disposed within the cell 70 having anidentification code of 11778154 is coated with a unique probe 78.

The “target” analytes 52-54 within the solution 60 are then mixed withthe functionalized microbeads 72-74. During the mixing of the “target”analytes 52-54 and the functionalized microbeads 72-74, the “target”analytes attach to the complementary probes 76-78, as shown forfunctionalized microbeads 72,73 having codes 12345678 and 34128913.Specifically, as shown in FIG. 19, “target” analytes 53 bonded withprobes 76 of the functionalized microbeads 72 having the code 12345678,and “target” analytes 52 bonded with probes 77 of the functionalizedmicrobeads 73 having the code 34128913. On the other hand, “target”analytes 54 did not bond with any probes, and not “target” analytes52-54 in the solution 60 bonded with probes 78 of the functionalizedmicrobeads 74 having the code 11778154. Consequently, knowing which“target” analytes attach to which probes along with the capability ofidentifying each probe by the encoded microbead, the results of theassay would show that the unknown “target” analytes in the solution 60includes “target” analytes 53, 54, as will be described in furtherdetail.

For example as discussed hereinbefore, each coded functionalizedmicrobead 72-74 has a unique probe 76-78, respectively bonded thereto,such as a portion of a single strand of DNA. Similarly, the “target”analytes 52-54 comprise a plurality of unknown and unique single strandsof DNA. These “target” analytes 52-54 are also processed with afluorescent, such as dyeing, such that the test molecules illuminate. Aswill be discussed hereinafter, the fluorescence of the “target” analytesprovide the means to identify, which functionalized microbeads 72-74have a “target” analyte attached thereto.

Once the reaction or combining is complete, the functionalizedmicrobeads 72-74 are rinsed off with a saline solution to clean off theuncombined “target” analytes 52-54. As shown in FIG. 20, thefunctionalized microbeads 72-74 may be placed in a tray 84 with grooves82 to allow the functionalized microbeads to be aligned in apredetermined direction, such as that described in U.S. patentapplication Ser. Nos. 10/661,234 (CyVera Docket No. CC-0038A),10/645,689 (CyVera Docket No. CV-0038), XX/XXX,XXX (CyVera Docket No.CV-0042), XX/XXX,XXX (CyVera Docket No. CV-0053PR), XX/XXX,XXX (CyVeraDocket No. CV-0082), and XX/XXX,XXX (CyVera Docket No. CV-0086PR), whichare all incorporated herein by reference. The grooves 82 may have holes(not shown) that provide suction to keep the functionalized microbeadsin position. Once aligned in the tray 84, the functionalized microbeads52-54 are individually scanned and analyzed by the bead detector 20,which includes one or more systems 15.

Alternatively, the functionalized microbeads 72-74 may be scanned andanalyzed in a flow cytometer 20 including one or more systems 15 asdepicted in FIG. 21.

As best shown in FIG. 22, each functionalized microbead 72-74 isdetected for fluorescence and analyzed to determine the identificationcode 58 of the functionalized microbeads. A light source (not shown) maybe provided to luminate the microbeads 72-74. Once the fluorescentmicrobeads 72-74 are identified and knowing which probe 76-78 (or singlestrand of DNA) was attached to each coded, functionalized microbead72-74, the bead detector 20 determines which “target” analytes 52-54were present in the solution 60. As described hereinbefore, the system15 illuminates the functionalized microbeads 72-74; detects a compositeX-ray diffraction pattern for each illuminated, functionalized microbead72-74; and decodes the composite X-ray diffraction pattern to determinethe code 58 of the functionalized microbead 72-74. Secondly, the beaddetector 20 includes a fluorescence detector 86 for measuring thefluorescence emanating from “target” analytes 52-54 attached to theprobes 76-78. The fluorescence meter 86 includes a lens 88 and opticalfiber 90 for receiving and providing the fluorescence from the “target”analyte 52-54 to the fluorescence meter.

Generally, the assay of the present invention may be used to carry outany binding assay or screen involving immobilization of one of thebinding agents. Such solid-phase assays or screens are well known in thechemical and biochemical arts. For example, such screening may involvespecific binding of cells to a molecule (e.g. an antibody or antigen)immobilized on a microbead in the assay followed by analysis to detectwhether or to what extent binding occurs. Alternatively, the beads maysubsequently removed from the assay for sorting and analysis via flowcytometry (see e.g. by Needels et al. (1993). Examples of biologicalcompounds that may be assayed or screened using the assay of the presentinvention include, e.g. agonists and antagonists for cell membranereceptors, toxins, venoms, viral epitopes, hormones, sugars, cofactors,peptides, enzyme substrates, drugs inclusive of opiates and steroids,proteins including antibodies, monoclonal antibodies, antisera reactivewith specific antigenic determinants, nucleic acids, lectins,polysaccharides, cellular membranes and organelles. In addition, thepresent invention may be used in any of a large number of well-knownhybridization assays where nucleic acids are immobilized on a surface ofa substrate, e.g. genotyping, polymorphism detection, gene expressionanalysis, fingerprinting, and other methods of DNA- or RNA-based sampleanalysis or diagnosis.

Any of the great number of isotopic and non-isotopic labeling anddetection methods well-known in the chemical and biochemical assay artmay be used to detect binding with the present invention. Alternatively,spectroscopic methods well-known in the art may be used to determinedirectly whether a molecule is bound to a surface coating in a desiredconfiguration. Spectroscopic methods include e.g., UV-VIS, NMR, EPR, IR,Raman, mass spectrometry and other methods well-known in the art. Forexample, mass spectrometry also is now widely employed for the analysisof biological macromolecules. The method typically involvesimmobilization of a protein on a surface of substrate where it is thenexposed to a ligand binding interaction. Following ligand binding (ornon-binding) the molecule is desorbed from the surface and into aspectrometer using a laser (see, e.g. Merchant and Weinberger, “Recentadvancements in surface-enhanced laser desorption/ionization-time offlight-mass spectrometry,” Electrophoresis 21: 1164-1177 (2000)). Themicrobeads in the assay of the present invention may be used assubstrates in the mass spectrometry detection methods described above.

Various aspects of the present invention may be conducted in anautomated or semi-automated manner, generally with the assistance ofwell-known data processing methods. Computer programs and other dataprocessing methods well known in the art may be used to storeinformation including e.g. microbead identifiers, probe sequenceinformation, sample information, and binding signal intensities. Dataprocessing methods well known in the art may be used to read input datacovering the desired characteristics.

The invention may be used in many areas such as drug discovery,functionalized substrates, biology, proteomics, combinatorial chemistry,DNA analysis/tracking/sorting/tagging, as well as tagging of molecules,biological particles, matrix support materials, immunoassays, receptorbinding assays, scintillation proximity assays, radioactive ornon-radioactive proximity assays, and other assays, (includingfluorescent, mass spectroscopy), high throughput drug/genome screening,and/or massively parallel assay applications. The invention providesuniquely identifiable beads with reaction supports by active coatingsfor reaction tracking to perform multiplexed experiments.

In particular, applications, uses, geometries and embodiments for theencoded element of the present invention may be the same as thatdescribed in the following patent applications which are allincorporated herein by reference in their entirety: U.S. patentapplication Ser. No. 10/661,234 (CyVera Docket No. CC-0038A), filed Sep.12, 2003, entitled “Diffraction Grating-Based Optical IdentificationElement”; U.S. patent application Ser. No. 10/661,031 (CyVera Docket No.CV-0039A) filed Sep. 12, 2003, entitled “Diffraction Grating-BasedEncoded Micro-particles for Multiplexed Experiments”; U.S. patentapplication Ser. No. 10/661,082 (CyVera Docket No. CV-0040), filed Sep.12, 2003, entitled “Method and Apparatus for Labeling Using DiffractionGrating-Based Encoded Optical Identification Elements”; U.S. patentapplication Ser. No. 10/661,115 (CyVera Docket No. CC-0041), filed Sep.12, 2003, entitled “Assay Stick”; U.S. patent application Ser. No.10/661,836 (CyVera Docket No. CV-0042), filed Sep. 12, 2003, entitled“Method and Apparatus for Aligning Microbeads in order to Interrogatethe Same”; U.S. patent application Ser. No. 10/661,254 (CyVera DocketNo. CV-0043), filed Sep. 12, 2003, entitled “Chemical Synthesis UsingDiffraction Grating-based Encoded Optical Elements”; U.S. patentapplication Ser. No. 10/661,116 (CyVera Docket No. CV-0044), filed Sep.12, 2003, entitled “Method of Manufacturing of a Diffractiongrating-based identification Element”; and U.S. patent application Ser.No. 10/763,995 (CyVera Docket No. CV-0054), filed Jan. 22, 2004,entitled, “Hybrid Random Bead/Chip Based Microarray”, U.S. ProvisionalPatent Applications, Ser. Nos. (CyVera Docket Nos. CV-0082 PR, CV-0083PR, CV-0084 PR, CV-0085 PR, CV-0086 PR, CV-0087 PR, CV-0088 PR, CV-0089PR, CV-0091 PR, and CV-0092).

In that case, the X-ray encoding technique of the present inventionwould be used instead of or in addition to the diffraction basedencoding described in the above patent applications. For example, asshown in FIG. 23, the substrate of binder material 5 may have at leastone diffraction grating 102 each having a predetermined number of bits(as described in the aforementioned patent applications) and at leastone composite X-ray diffraction pattern as described herein. Thematerials 1-4 provide the X-ray diffraction pattern when illuminated byan X-ray beam 104, and the incident light 106 provides the opticaloutput signal from the diffraction grating 102. For example, the X-raydiffraction pattern may add an additional bit to the code provided bythe optical output signal. Thus, the X-ray diffraction pattern adds anadditional level of code multiplexing.

Some current techniques used in combinatorial chemistry or biochemistryare described in U.S. Pat. No. 6,294,327, entitled “Apparatus and Methodfor Detecting Samples Labeled With Material Having Strong LightScattering Properties, Using Reflection Mode Light and DiffuseScattering”, issued Sep. 23, 2001 to Walton et al.; U.S. Pat. No.6,242,180, entitled “Computer Aided Visualization and Analysis Systemfor Sequence Evaluation”, issued Jun. 5, 2001, to Chee; U.S. Pat. No.6,309,823 entitled “Arrays of Nucleic Acid Probes for AnalyzingBiotransformation of Genes and Methods of Using the Same”, Oct. 30,2001, to Cronin et al.; U.S. Pat. No. 6,440,667, entitled “Analysis ofTarget Molecules Using an Encoding System”; U.S. Pat. No. 6,355,432,entitled “Products for Detecting Nucleic Acids”; U.S. Pat. No.6,197,506, entitled “Method of Detecting Nucleic Acids”; U.S. Pat No.6,309,822, entitled “Method for comparing copy number of nucleic acidsequences”; U.S. Pat. No. 5,547,839, entitled “Sequencing of surfaceimmobilized polymers utilizing micro-fluorescence detection”, U.S. Pat.No. 6,383,754, entitled “Binary Encoded Sequence Tags”, and U.S. Pat.No. 6,383,754, entitled “Fixed Address Analysis of Sequence Tags”, whichare all incorporated herein by reference to the extent needed tounderstand the present invention.

The invention can be used in combinatorial chemistry, active coating andfunctionalized polymers, as well as immunoassays, and hybridizationreactions. The invention enables millions of parallel chemicalreactions, enable large-scale repeated chemical reactions, increaseproductivity and reduce time-to-market for drug and other materialdevelopment industries.

As discussed hereinbefore, although a fluorescent label is probably mostconvenient, other sorts of labels, e.g., radioactive, enzyme linked,optically detectable, or spectroscopic labels may be used. Anappropriate detection method applicable to the selected labeling methodcan be selected. Suitable labels include radionucleotides, enzymes,substrates, cofactors, inhibitors, magnetic particles, heavy metalatoms, and particularly fluorescers, chemiluminescers, and spectroscopiclabels. Patents teaching the use of such labels include U.S. Pat. Nos.3,817,837; 3,850,752; 3,939,350; 3,996,345; 4,277,437; 4,275,149; and4,366,241.

With an appropriate label selected, the detection system best adaptedfor high resolution and high sensitivity detection may be selected. Asindicated above, an optically detectable system, e.g., fluorescence orchemilumnescence would be preferred but is not required. Other detectionsystems may be adapted to the purpose, e.g., electron microscopy,scanning electron microscopy (SEM), scanning tunneling electronmicroscopy (STEM), infrared microscopy, atomic force microscopy (AFM),electrical conductance, and image plate transfer.

Unless otherwise specifically stated herein, the term “microbead” isused herein as a label and does not restrict any embodiment orapplication of the present invention to certain dimensions, materialsand/or geometries.

The dimensions and geometries for any of the embodiments describedherein are merely for illustrative purposes and, as such, any otherdimensions may be used if desired, depending on the application, size,performance, manufacturing requirements, or other factors, in view ofthe teachings herein.

It should be understood that, unless stated otherwise herein, any of thefeatures, characteristics, alternatives or modifications describedregarding a particular embodiment herein may also be applied, used, orincorporated with any other embodiment described herein. Also, thedrawings herein are not drawn to scale.

Although the invention has been described and illustrated with respectto exemplary embodiments thereof, the foregoing and various otheradditions and omissions may be made therein and thereto withoutdeparting from the spirit and scope of the present invention.

1-37. (canceled)
 38. A composition comprising: an item; and an opticalidentification element that is physically associated with the item, theoptical identification element comprising: a binder material; and one ormore materials embedded in the binder material, the one or morematerials providing a composite X-ray diffraction pattern whenilluminated by an X-ray beam, the composite X-ray diffraction patternbeing indicative of a code, the code relating to information about theitem.
 39. The composition of claim 38, wherein the code includes abinary or higher order code.
 40. The composition of claim 38, whereinthe code includes a binary code having a number of bits that correspondto a number of unique Debye-Scherrer diffraction patterns in thecomposite X-ray diffraction pattern.
 41. The composition of claim 38,wherein the code is a binary code that is arranged in a protocolincluding one or more error-check bits and a plurality of data bits. 42.The composition of claim 38, wherein the one or more materials eachinclude a powdered crystal material.
 43. The composition of claim 38,wherein the binder material is selected from glass, plastic, one or morepolymers, and combinations including one or more of the foregoing. 44.The composition of claim 38, wherein the optical identification elementis shaped as a microbead.
 45. The composition of claim 38, wherein theoptical identification element is shaped as a macrobead.
 46. Thecomposition of claim 38, wherein the binder material is in the form of athread or fiber. 47 The composition of claim 38, wherein the item isselected from the group consisting of: large objects, small objects,products, solids, powders, liquids, gases, plants, pharmaceuticals,currency, ID cards, minerals, cells and/or animals.
 48. The compositionof claim 38, wherein the item is a chemical.
 49. The composition ofclaim 38, wherein the item comprises a nucleic acid probe.
 50. Thecomposition of claim 49 wherein the nucleic acid probe is hybridized toa target nucleic acid.
 51. The composition of claim 38 wherein theoptical identification element is configured for labeling the item forat least one of sorting, tracking, identifying, verifying, andauthenticating the item.
 52. The composition of claim 38 wherein thecode includes an error check portion configured to ensure that the codeis accurate.
 53. The composition of claim 38 wherein the at least onematerial includes a plurality of materials, each material having apredetermined diffraction pattern configured for a coding system. 54.The composition of claim 53 wherein the plurality of materials is aplurality of crystal materials, each crystal material having apredetermined Debye-Scherrer X-ray diffraction pattern configured forthe coding system.
 55. The composition of claim 38 wherein the itemincludes material that is one of transparent to the X-ray beam andsubstantially transparent to the X-ray beam.
 56. The composition ofclaim 38 wherein the binder material either does not diffract the X-raybeam or diffracts the X-ray beam in a known manner.
 57. The compositionof claim 41 wherein the code includes start and stop bits.